Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
  • C08G73/0644—Poly(1,3,5)triazines

Definitions

• the polymers are prepared by polycondensation of a 2,4-dihydrazino-s-triazine and an aromatic dicarboxylic acid dihalide at moderate temperatures while removing the exothermic heat of the reaction and in the presence of an acid acceptor.
• the high molecular weight polymer product can be wetspun or dry-spun to form useful filaments, fibers, films, ribbons or the like.
• Suitable 2,4-dihydrazino-s-triazines (II) are those substituted in the 6-position by the radical R which, represents the following groups: i I
• a. lower alk yl ie an alkyl group of l to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl or isobub. phe'nyl
• a c. lower alkoxy i.e. an alkoxy group of 1- to 4 carbon atoms' such as methoxy, ethoxy, propoxy, butoxy or isobutoxy
• phenoxy e. dialkylamino in which the'alkyl groups are preferably lower alkyl of 1 to 4 carbon atoms and may be the same or different to provide a total of 2 to 8 carbon atoms, for example dimethylaminmdiethylamino, dipropylamino, dibutylamino, diisopropylamino, diisobutylamino and- N-methyl-N- ethyl-amino; fQ N-piperidyl; g. N-morpholyl; and h. phosphonic acid dialkyl esters of 2 to 8 carbon atoms, for example the dimcthyl- 'or diethylphosphonic acid esters.
• a 1 phosphonic acid dialkyl esters of 2 to 8 carbon atoms, for example the dimcthyl- 'or diethylphosphonic acid esters.
• 2,4-dihydrazinodimethylamino-s-triazine 2,4-dihydrazino-6-meth oxy-s-triazine; 2,4-dihydrazino-6-butoxy-s triazine; 2,4-dihydrazino-6-phenyLs-triazine, 2.4-dihydrazino-6-(phosphonic .acid diethyl ester)-striazine; 2,4-dihydrazino-6-morpholino-s triazine; and 2,4-dihydrazino-6-phenoxy-s-triazine.
• The'2,4.-dihyd razino-s-triazines are easily accessible by following knownnmethods ofpreparation.
• cyanuric acid ,chloride with the desired dialkylamine and then treat the resulting 2,4-dich1oro-6-dialk ylamino-s-triazine, with hydrazine; see German published application (DOS) No. 2,129,995 and US. Pat. No. 3,087,910.
• DOS German published application
• the 6- alkoxy derivative can be produced from cyanuric acid chloride, the corresponding alkanol and hydrazine" See German published application (DOS) No.
• the 6-alkyl derivatives are obtainable by reaction of hydrazine with the corresponding 2,4-dichlo ro-6-alkyls-triazines inaccordancewith Reimschuesselet al., J. Am. Chem. Soc., Vol. 82, p. 3756 (1960).-
• the 2,4- dichloro-6-alkyl-s triazines are easily accessible from cyanuric chloride and Grignard compounds; see l-lirt et al., Helv. Chirn. Acta., Vol. 33, p. 1368 1950).
• aromatic dicarboxylic acid dihalides which may 'be employed. preferably those represented by the formula inwhich R is a divalent aromatic radical of 6 to 15 carbon atoms and Hal is a bromine or chlorine atom.
• Suitablearomatic radicals are especially phenyl, 'diphenyl O1 I I 1 in which v.15 one our; bridges 0 's-.
• polyacyl-dihydrazino-s-triazines of the invention can be extruded or spun into filaments and films with good commercial properties.
• Those polymers which can be processed into useful filamentary or filmaceous products of high strength are as follows:
• the polyacyl-2,4-dihydrazino-s-triazine of the invention can be synthesized either by a solution polycondensation or by the so-called interfacial polycondensation process.
• the reaction between the 2,4-dihydrazino-s-triazines and the dicarboxylic acid dihalides as the initial monomers proceeds relatively rapidly in most cases.
• stirring or continuous mixing is necessary primarily for the purpose of avoiding differences in concentration and to accelerate the reaction and the heat exchange.
• the reaction naturally takes place at the interface and it is therefore especially desirable to provide good mixing or stirring and advantageously an emulsifier or the like to facilitate material interchange between both phases.
• the mixer is ordinarily one which is operated at a speed of about 500 to l5,000 r.p.m.
• the added emulsifier is preferably used in an amount of about 0.1 to 1% by weight, with reference to the water, and can be easily selected from commercially available materials, for example such surface active agents as so dium lauryl sulfate, EMULPHOR EL (a polyoxyeacid-2,4-dihyacid-2,4-dihy- 4 thylated vegetable oil) and INTRASOL WL (an oxyethylated product with OH No. F3-F6).
• the cooling also serves to withdraw the frictional heat arising from the mixing system.
• Any suitable cooling medium can be employed for removing heat from the reaction mixture, preferably using conventional indirect heat exchange apparatus where required in large scale operations. On a laboratory basis, a cooling bath around the reaction vessel is generally sufficient.
• the reaction components are dissolved together in a suitable inert organic solvent and reacted in a homogeneous phase.
• Suitable solvents for this single phase polycondensation are especially the aprotic solvents such as dimethyl acetamide, N-methylpyrrolidone, hexamethylphosphoric acid triamide, sulfolane (tetrahydrothiophene-l,l-dioxide) or tetramethylurea.
• Those solvents which are especially preferred are hexamethylphosphoric acid triamide, dimethyl acetamide and N-methyl-pyrrolidone. These solvents should be as dry as possible, eg with a water content of less than 0.01% by weight. Anhydrous solvents are thus especially preferred.
• Acid acceptors which are soluble in such organic solvents are for example the tertiary organic nitrogen bases such as pyridine and its methyl derivative (picoline) or triethylamine and similar tertiary amines. While it may be preferred to use those acid acceptors which are soluble in the particular solvent system chosen for the reaction medium, one may also use insoluble acid acceptors for binding the halogen halide split off in the reaction, e.g. such as soda (sodium carbonate), lithium carbonate, alkali bicarbonates and acetates. In this case, these insoluble acid acceptors or binding agents are suspended in very finely divided form in the organic phase.
• tertiary organic nitrogen bases such as pyridine and its methyl derivative (picoline) or triethylamine and similar tertiary amines.
• insoluble acid acceptors for binding the halogen halide split off in the reaction e.g. such as soda (sodium carbonate), lithium carbonate, alkal
• Aprotic solvents such as hexamethylphosphoric acid triamide, dimethyl acetamide, N-methylpyrrolidone and tetramethylurea, which possess a tertiary nitrogen atom, may also be simultaneously employed to bind the hydrogen halide being set free, e.g. hydrogen chloride.
• the degree of polycondensation of the polyacyl-2,4- dihydrazino-s-triazines of the invention when carrying out a solution polycondensation, depends not only upon the reaction medium itself but also upon the concentration of the monomeric reactants, the reaction temperature and the period of time for the reaction.
• the viscosity of the reaction medium increases with an increase in the monomer concentration, there is a limit to the extent by which the degree of polycondensation can be extended through a greater concentration of monomers due to the fact that there is a corresponding limit on the capacity of available equipment for stirring or mixing the reaction medium.
• the reaction temperature for the solution polycondensation process should be about lOC. to +60C., preferably about 5C. to 40C. As a rule, the degree of polycondensation increases with increasing reaction temperatures, but it is undesirable to exceed the cited temperatures because the polymer tends to form a gel or semi-solid mass.
• the degree of polycondensation is dependent upon the length of the reaction. In general, a reaction time of about 2 to 16 hours is needed to obtain polymers having satisfactory fiberand film-forming properties.
• a further especially preferred embodiment of the invention resides in carrying out the polycondensation in two inert solvents which are not miscible with each other. It is apparent in this case that the reaction takes place largely at the interface between the two solvents.
• one phase consists of an inert .solvent for the acyl dihalide, i.e. the dicarboxylic acid dihalide monomer, while the other phase consists of the solvent for the 2,4-dihydrazino-s-triazine monomer.
• the acid acceptor is preferably dissolved in the same .solvent used for the 2,4-dihydrazino-s-triazine.
• Suitable solvents for the acyl dihalide the following are given by way of example: methyl acetate, ethyl acetate, tetrahydrofuran, tetrahydropyran, dioxane, hexane, heptane, cyclohexane, decalin, chloroform, carbon tetrachloride, benzene, toluene, methylene chloride, monochlorobenzene and acetonitrile.
• solvents may be classified as hydrocarbons and chlorinated hydrocarbons, and suitable solvents of this one phase can be readily selected for the acyl dihalide monomer based upon its capacity to dissolve this monomer while being immiscible with the inert solvent of the other phase.
• Solvents used for the second phase i.e. for the 2,4- dihydrazino-s-triazine and the acid acceptor. are preferably selected from the class consisting of water, N- dimethylacetamide, hexamethylphosphoric acid triamide, N-methylpyrrolidone and tetramethylurea.
• the solvents given in each case are naturally combined so as to fulfill the condition that they form two immiscible phases as liquid solvents at the reaction temperature.
• Especially preferred mixtures are those obtained by using water for one phase and toluene, benzene, hexane, carbon tetrachloride, methylene chloride or mixtures of these organic solvents for the other phase.
• one of the two phases consists of an aqueous solution of the 2,4-dihydrazino-s-triazine and the acid acceptor while the other phase consists of benzene, toluene, hexane, carbon tetrachloride, methylene chloride or mixtures thereof.
• the acid acceptor in this case, the alkali metal carbonates and bicarbonates. particularly sodium or potassium carbonate and bicar bonate, have been found to be especially useful. Strong bases are also recommended as the acid acceptor under circumstances where there is a sharp distinction between the two liquid phases of the reaction mixture.
• strong bases become very useful provided that the components forming the organic phase and the aqueous phase remain substantially completely insoluble in each other, i.e. when the miscibility of the two phases is as small as possible. It is then possible to avoid any extensive saponification of the of the dicarboxylic halide reactant.
• the suitability of various common acid acceptors and the choice between strong or weak bases can be readily determined by a simple preliminary test.
• Another suitable polycondensation technique for the production of the polymers of the invention resides in the use of water as one phase and a water-miscible, inert organic solvent as the second phase with the proviso that the water-miscibility of the inert organic solvent is completely or practically completely prevented by the addition of a so-called salting-out agent.
• the principle of separating a normally miscible organic solvent from water by adding a salting-out agent is well known and does not require elaboration because it merely represents another means of forming the twophase reaction mixture.
• one of the two phases in this case consists of an aqueous triazine solution which contains the salting out agent, and the other phase consists of a solution of the dicarboxylic halide in an inert organic solvent.
• strong mixing is recommended in this two-phase technique.
• any salting-out agent should also be substantially inert with respect to the monomers and the reaction products under the reaction conditions. Otherwise. the salting-out agent may be any water-soluble salt commonly used for this purpose.
• the acid acceptor may also simultaneously serve the function of the salting-out agent.
• Soda. i.e. sodium carbonate is especially 7 useful as both acid acceptor and salting-out agent.
• the choice of the salting-out agent and its required amount depends upon the particular solvent and its miscibility in water, something which can be easily determined-by a routine test if not already known as in most cases.
• the reaction period should be at least about to 30 minutes to provide a satisfactory fiber-forming and film-forming polymer.
• Polyacyl-2,4-dihydrazino-s triazines of different molecular weights are produced within the scope of the invention according to the.particular method of polycondensation.
• the molecular weight is also influenced by the monomeric reactants but can be varied over a relatively wide range even when starting with the same monomers.
• the polycondensate product has a reduced viscosity (m of about 0.9 to 11, measured at C. as a solution of 1 gram of the polymer in 100 ml. of 98% formic acid.
• the polymers of the invention are colorless to yellow and are soluble in dimethyl sulfoxide, dimethyl formamide,' N-methyl-pyrrolidone, hexamethyl-phosphoric acid triamide, sulfuric acid, formic acid and sodium or potassium hydroxide agueous solutions. Some of the polymers are decomposed or degraded in concentrated caustic potash solution, i.e. cone. KOl-l in water.
• the essentially linear polymers of the invention can be formed into useful filaments, fibers, foils and the like with valuable special properties.
• the forming, shaping, extrusion or so-ealled spinning of the polymer can be carried out according to the wet process or the dry process.
• wet spinning can take place by dissolving the polymer in aqueous caustic potash (KOH) or caustic soda (NaOH) and then solidifying the extruded filaments or films in an acetic acid bath.
• KOH caustic potash
• NaOH caustic soda
• Especially suitable polymer solvents for carrying out the dry spinning process are dimethylacetamide. N-methylpyrrolidone and dimethyl formamide.
• EXAMPLE 1 In a 500 ml. flask equipped with a mixer and a thermometer while introducing nitrogen as an inert atmosphere, there were dissolved 12.5 g. LiCl and 92.5 millimols (17.02 g.) of 2,4-dihydrazino-6-dimethylaminos-triazone in 226 ml. of absolute, amine-free dimethylacetamide. The resulting solution was then cooled down to +5C., and under strong mixing and flushing with nitrogen, 92.5 millimols (27.28 g.) of diphenylether-4,4'-dicarboxylic acid dichloride were added to the solution over a period of about 5 minutes such that the temperature was maintained at about 30C.
• reaction mixture became highly viscous after a relatively short period of time. Mixing was continued for about 16 hours, and the mixture was then poured into an aqueous NaHCO -solution wherein the polymer precipitated out and the HCl produced by the condensation became neutralized.
• the product was washed with water and methanol and dried at 60C. under vacuum.
• the viscosity (1p was 4.9.
• EXAMPLE 2 The polycondensation was carried out in solution as described in Example 1. In this case, however, the solvent used was an absolute, amine-free N-methylpyrrolidone-(2). The reaction period was 2 hours. The resulting polycondensate had a reduced viscosity rp 6.1.
• EXAMPLE 3 2O millimols (3.68 g.) of 2,4-dihydrazino-6-dimethylamino-s-triazine, g. LiCl and 3.6 g. of NaHCO- as an acid acceptor were dissolved in 750 ml. of H 0 and the resulting solution placed in a vessel equippped with a Kotthoff mixer. While stirring and with outer cooling of the vessel, 20 millimols (5.9g.) of diphenylether-4,4'- dicarboxylic acid dichloride were dissolved in 750 ml. of absolute benzene and added in a jet stream, the mixture being stirred at 2800 r.p.m.
• EXAMPLE 4 50 millimols (9.2 g.) of 2,4-dihydrazino-6-dimethylamino-s-triazine were dissolved in a nitrogen atmosphere in 100 ml. absolute, amine-free dimethylacetamide and cooled with mixing to +5C. Then, in a period of about 5 minutes, 50 millimols (14.75 g.) of diphenylether4,4'-dicarboxylic acid dichloride were continuously added whereby the temperature rose to 3035C. After mixing for 16 hours, the viscous reaction mixture was poured into an aqueous sodium bicarbonate solution.
• Rf is: where R is: t Solvent Mol/l l7 CH, 7 lsophthal- 'Tolue'ne/Wasser v 0.040 2.72
• the reaction mixture was then stirred for another 15 hours at room temperature after which it was poured into 500 ml. of water with intensive mixing and then neutralized with sodium bicarbonate.
• the resulting polymer which deposited in fiber-like form was thoroughly washed with water and methanol and then dried under vacuum at The resulting colorless polymer exhibited a reduced viscosity (n -11) of 6.38.
• EXAMPLE 22 In a 250 ml. three-necked flask equipped with a mixer and thermometer as in the preceding example. 10.4 g. of water-free lithium chloride and 50 millimols (l 1.66 g.) of 2.4-dihydrazino-6-phenoxy-s-triazine were dissolved in 100 ml. absolute dimethylacetamide while leading in nitrogen to exclude atmospheric moisture. The solution was cooled to 10C. and combined in portions with 50 millimols (14.75 g.) of solid diphenylether-4.4-dicarboxylic acid dichloride such that the reaction temperature did not rise above C.
• the viscous polymer solution was poured into water with intensive stirring and then neutralized with sodium carbonate.
• the deposited colorless polymer was washed several times with water and methanol and dried under vacuum at 70C.
• the reduced viscosity (m of the polymer was 2.53.
• the reduced viscosity of the polymer product was EXAMPLE 24 15 millimols (3.49 g.) of 2.4-dihydrazino-6-phenoxys-triazine were dissolved at 60C. in 900 m1. of a 15% aqueous lithium chloride solution. then cooled to 20C. and placed together with an aqueous solution of millimols (2.52 g.) of sodium bicarbonate into the reaction kettle. The solution was strongly mixed with a so-called mixing siren" (2.8'10 rpm.) and combined into a batch with a solution of 15 millimols (3.04 g.) ofisophthaloyl chloride in 900 ml. of absolute hexane. Under 12 water cooling. this mixture was further mixed for another 30 minutes, then filtered with suction and washed several times with water and methanol. The colorless polymer was finally dried under vacuum at C.
• the reduced viscosity of the polymer product was 1.93.
• EXAMPLE 25 A. Production of 2.4-dihydrazino-6-phosphonic acid diethyl ester-s-triazine 0.1 mol (29.9 g.) of diphenoxy-chloro-s-triazine and 0.1 1 mol (18.4 g.) of triethylphosphite were placed in a 250 ml. three-necked flask provided with a mixer. cooler, thermometer and a nitrogen supply line. Under a stream of N the reaction mixture was heated slowly to 140C. and stirred at this temperature for 2 hours. It was then cooled to 120C. and the excess triethylphosphite distilled off under vacuum. As the residue. there was obtained a yield of of 2.4-diphenoxy-6-phosphonic acid diethyl ester-s-triazine with a melting point of 7779C.
• the above-noted polymers may be wet spun and/or dry spun into filaments which are readily stretched in a conventional manner to develop valuable fibrous properties. Moreover. one may also extrude and stretch films of these new polymers to obtain relatively strong and stable sheets. ribbons or similar products. It is especially useful to obtain such fibers or films from polymers which have a reduced viscosity (measured as in all of the examples) of at least about 2 preferably about 2 to 1 1.
• R is a substituent selected from the group consisting of dimethylamino, methoxy, butoxy, phenyl, phosphonic acid diethyl ester, morpholino and phenoxy.
• a process as claimed in claim 8 wherein said inert organic solvent is selected from the group consisting of dimethylacetamide. N-methylpyrrolidone, hexamethylphosphoric acid triamide and mixtures thereof.
• vent mixture eonsists essentially of a mixture of water methylene chloride and mixtures thereof.

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• 1973
  • 1973-05-24 DE DE2326473A patent/DE2326473A1/de active Pending
• 1974
  • 1974-05-20 US US471504A patent/US3920611A/en not_active Expired - Lifetime
  • 1974-05-22 FR FR7417953A patent/FR2230681B3/fr not_active Expired
  • 1974-05-24 JP JP49058660A patent/JPS5022090A/ja active Pending
  • 1974-05-24 GB GB2331274A patent/GB1425535A/en not_active Expired

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